CN107325270A - A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type and preparation method thereof - Google Patents
A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type and preparation method thereof Download PDFInfo
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- CN107325270A CN107325270A CN201710499410.9A CN201710499410A CN107325270A CN 107325270 A CN107325270 A CN 107325270A CN 201710499410 A CN201710499410 A CN 201710499410A CN 107325270 A CN107325270 A CN 107325270A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention discloses a kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, it is characterized in that：By 25.92~43.20 mass parts copoly type sulfonate, 443.66~552.18 mass parts binary of fatty acids, 292.56~423.06 mass parts polyalcohols, 119.99~154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants and 0.60~1.06 mass parts of catalyst A is through esterification and removes moisture, it is again to be made through polycondensation, at the fire-retardant sulphonate-base PEPA average functionality 2.0 of Halogen copoly type of the present invention, 25 DEG C of viscosity≤10000 mPaS, 55~65mgKOH/g of hydroxyl value, the mgKOH/g of acid number≤2, and at 25 DEG C of normal temperature storage 6 months without hydrolysis；Available for coating, adhesive, fabric coating and finishing agent, leather finishing agent, sheet surface treating agent etc.；Synthesis technique is simply controllable, environmental protection, practical.
Description
Technical field
The invention belongs to organic high molecular compound and its preparation, it is related to a kind of fire-retardant sulphonate-base polyester of Halogen copoly type
Polyalcohol and preparation method thereof.The fire-retardant sulphonate-base PEPA of Halogen copoly type prepared by the present invention, it is adaptable to prepare nothing
Halogen extinguishing waterborn polyurethane resin, can be widely applied to coating, adhesive, fabric coating and finishing agent, leather finishing agent, paper
Surface conditioning agent etc..
Background technology
Using water-based halogen-free flame retardant polyurethane resin as the flame retardant coating of base rubber, it is widely used in yarn fabric, high-grade paper, skin
The durable flame-proof fire prevention processing of leather goods and wood furniture etc..In addition, be alternatively arranged as flame-retarding adhesive, for it is electric,
The fields such as photovoltaic generation.Water-based halogen-free flame retardant polyurethane resin is divided into solvent-borne type (oiliness) and water-dispersion type (aqueous).Solvent-borne type
Flame-retardant coatings glue has the advantages that good leveling property, film forming speed be fast, film sense is smooth, but the use of a large amount of organic solvents, halogen resistance
The addition of agent is fired, severe contamination environment is detrimental to health.In recent years, water-based halogen-free flame-retardant coatings glue is easy to dilution because having
The advantages of with coating, without combustion explosion danger, VOC low, non-environmental-pollution, the accreditation in market is received, on many fabrics all
Realize the replacement to solvent based flame-retardant coating adhesive.Thus preparing the water-based halogen-free flame retardant polyurethane resin of high solids content turns into not
Come the inexorable trend developed.
The existing halogen-free flameproof waterborne polyurethane resin technology for preparing high solids content, is in preparation process, to add one
The quantitative PEPA containing sulphonate-base, in order to obtain anti-flammability, adds the substantial amounts of polyester polyols with ignition-proof element again
Alcohol.The technical problem produced therefrom is：1) it is dilute after addition because the PEPA containing sulphonate-base is free of ignition-proof element
The concentration of system ignition-proof element has been released, has been caused on using waterborne flame retardant polyurethane resin as the oxygen index (OI) of the flame retardant coating of base rubber not
Go, anti-flammability is deteriorated；2) after PEPA containing sulphonate-base and the PEPA mixing with ignition-proof element, due to this two
The viscosity, density, polarity for planting PEPA are different, it may appear that poor compatibility, uneven phenomenon are mixed, so as to influence aqueous
The quality of polyurethane coating glue.Preparing the method for above two PEPA has：CN1720278A discloses a kind of sulfonate
The preparation method of functional polyester polyalcohol, using unsaturated carboxylic acid or derivatives thereof, polyalcohol, lactone and sulfonating agent system
Standby, the addition of PEPA energy can improve the solid content of waterborne flame retardant polyurethane resin, but not have anti-flammability, on the contrary
The content of ignition-proof element in meeting diluted system, so as to reduce the resistance using waterborne flame retardant polyurethane resin as the flame retardant coating of base rubber
Combustion property.CN103044673A discloses a kind of preparation method of response type halogen-free phosphorus-containing fire retardant PEPA, and the method uses two
First acid, dihydric alcohol (straight chain type), halogen-free phosphorus-containing copoly type fire retardant copolymerization are formed.In polyester polyol molecule chain prepared by the method
Containing ignition-proof element but without sulphonate-base, 30% or so is can only achieve with its aqueous polyurethane coating solid content prepared,
The aqueous polyurethane coating of high solids content (60%) is prepared, another PEPA containing sulphonate-base must also be added, so
The reduction of ignition-proof element concentration can be caused, the fire resistance of coating glued membrane below is influenceed, and use straight dihydric alcohol, the polyester of preparation
Polyalcohol hydrolytic resistance is poor.
The content of the invention
The purpose of the present invention is intended to overcome that above-mentioned of the prior art not enough there is provided a kind of fire-retardant sulfonate of Halogen copoly type
Base PEPA and preparation method thereof.The present invention is accessed when synthesizing halogen-free antiflaming polyester polyalcohol directly on strand
Sulphonate-base, so that providing a kind of under the premise of ensureing that anti-flammability is preferable and can improve the solid content of waterborne polyurethane resin
The fire-retardant sulphonate-base PEPA of Halogen copoly type and preparation method thereof.
Present disclosure is：A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, it is characterized in that：By 25.92
~43.20 mass parts copoly type sulfonate, 443.66~552.18 mass parts binary of fatty acids, 292.56~423.06 mass parts
Polyalcohol, 119.99~154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants and 0.60~1.06 mass parts of catalyst A are mixed
Close, through esterification and remove moisture, then through polycondensation, the obtained fire-retardant sulphonate-base PEPA of Halogen copoly type；
The copoly type sulfonate has following general structure：
In formula：Me is chemical element Na, K or Li, R1For C2-9H4-18Alkylidene, R2For C2-9H4-18Alkylidene, and
R in same molecule1With R2Relation is：R1=R2Or R1≠R2；I.e.：Can be R in same molecule1=R2=-CH2CH2-, or：
R1=-CH2CH2- and
The binary of fatty acids is one or both of succinic acid, glutaric acid, adipic acid, azelaic acid and SA
Mixture above, preferably adipic acid；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2-
In propane diols, 1,3 butylene glycol, 1,2 pentanediols one in one or more kinds of and glycerine, trimethylolpropane, pentaerythrite
Plant or two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl benzene
Mixture more than one or both of base hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and chlorine
Change any of stannous etc. or two or more mixtures；
In present disclosure：In the polyalcohol, the mol ratio of glycol and triol, tetrol or triol+tetrol can be：
Glycol：(triol, tetrol or triol+tetrol)=100：5~15, mol ratio preferably is 100：5~8.
In present disclosure：The average functionality of the fire-retardant sulphonate-base PEPA of Halogen copoly type be 2.0,
Viscosity is at 25 DEG C≤10000mPaS, 55~65mgKOH/g of hydroxyl value, acid number be≤2mgKOH/g, and in 25 DEG C of conditions of normal temperature
It is lower to store 6 months without hydrolysis phenomena.
In present disclosure：The copoly type sulfonate can be prepared with following method：By 1000 mass parts isophthalic
Dicarboxylic acid dimethyl ester -5- sulfonate, 230~470 mass parts dihydric alcohols and 1.2~1.6 mass parts of catalyst B inputs have rectifying column
Reactor A in, be passed through nitrogen, stir, the material of reactor A since room temperature to distillating methanol 140~150 DEG C, when
Distillate liquid measure it is seldom when (reaction time is usually 2~3 hours), in the case where control rectifying capital temperature is no more than 65 DEG C, then
230~235 DEG C are to slowly warm up to from 140~150 DEG C, untill it can not go out liquid (reaction time is usually 3~4 hours), is stopped
Only react, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid two
One or more kinds of mixtures, preferably isophthalic in methyl esters -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums
Dicarboxylic acid dimethyl ester -5- sodium sulfonates；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- third
One or more kinds of mixture in glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is acetic acid salt compounds, is lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
Middle one or more kinds of mixture.
The present invention another content be：A kind of preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type, its
It is characterized in that step is as follows：
A, prepare copoly type sulfonate：
By 1000 mass parts DMIP -5- sulfonate, 230~470 mass parts dihydric alcohols and 1.2~1.6
Mass parts of catalyst B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, the material of reactor A from room temperature to
140~150 DEG C start to distillate methanol, when distillate liquid measure it is seldom when (reaction time is usually 2~3 hours), control rectifying column
Top temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230~235 DEG C from 140~150 DEG C, (anti-untill it can not go out liquid
It is usually 3~4 hours between seasonable), stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made, it is standby；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid two
One or more kinds of mixtures, preferably isophthalic in methyl esters -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums
Dicarboxylic acid dimethyl ester -5- sodium sulfonates；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- third
One or more kinds of mixture in glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is acetic acid salt compounds, is lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
One or more kinds of mixture in；
B, prepare the fire-retardant sulphonate-base PEPA of Halogen copoly type：
(a) feed proportioning：
Weigh the mass parts copoly type sulfonate of raw material 25.92~43.20,443.66~552.18 mass parts di-fatties
Acid, 292.56~423.06 mass parts polyalcohols, 119.99~154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants, 0.60~
1.06 mass parts of catalyst A, it is standby；
The copoly type sulfonate is produced by step a；
The binary of fatty acids is any of succinic acid, glutaric acid, adipic acid, azelaic acid and SA or two
Plant the mixture of the above；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2-
In propane diols, 1,3 butylene glycol, 1,2 pentanediols one in one or more kinds of and glycerine, trimethylolpropane, pentaerythrite
Plant or two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl benzene
Mixture more than one or both of base hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and chlorine
Change any of stannous etc. or two or more mixtures；
(b) the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared：
By each raw material and consumption described in step (a) feed proportioning, put into the reactor B of rectifying column, be passed through nitrogen,
Stirring, the material of reactor B is from room temperature, when temperature reaches 110~120 DEG C by room temperature in reactor B, when starting to distillate water
Rise, the insulation reaction time is 2~3 hours, when control rectifying column head temperature remains at 80~105 DEG C during reaction, when
When rectifying column head temperature is reduced to less than 75 DEG C, then (slow) rise temperature reaches 160 DEG C, continues insulation reaction 1 hour, so
Slowly be warming up to 180 DEG C afterwards, continue insulation reaction after 3~4 hours, then be slowly warming up to 200 DEG C, to continue insulation reaction 2~3 small
When, then be slowly warming up to 230~240 DEG C, continue insulation reaction 2~3 hours, during reaction when the control of reaction mass acid number≤
15mgKOH/g, and the rectifying column head temperature of reactor B is when being down to less than 75 DEG C, stops heating, reaction mass is down into 220
DEG C when be incubated, and slow suction is to -0.090~-0.095MPa, as acid number≤2mgKOH/g, stops reaction, cold
But, that is, the fire-retardant sulphonate-base PEPA of Halogen copoly type is made.
In another content of the present invention：In the polyalcohol, the mol ratio of glycol and triol, tetrol or triol+tetrol can
Think：Glycol：(triol, tetrol or triol+tetrol)=100：5~15, mol ratio preferably is 100：5~8.
In another content of the present invention：The average function of the fire-retardant sulphonate-base PEPA of obtained Halogen copoly type
Degree be 2.0, viscosity be at 25 DEG C≤10000mPaS, 55~65mgKOH/g of hydroxyl value, acid number be≤2mgKOH/g, and in normal temperature
6 months are stored under the conditions of 25 DEG C without hydrolysis phenomena.
In another content of the present invention：The copoly type sulfonate can be the copoly type sulfonic acid for having following general structure
Salt：
In formula：Me is chemical element Na, K or Li, R1For C2-9H4-18Alkylidene, R2For C2-9H4-18Alkylidene, and
R in same molecule1With R2Relation is：R1=R2Or R1≠R2；I.e.：Can be R in same molecule1=R2=-CH2CH2-, or R1
=-CH2CH2- and
Compared with prior art, the present invention has following features and beneficial effect：
(1) the fire-retardant sulphonate-base PEPA of Halogen copoly type of the invention, by copoly type sulfonate with containing branch
When dihydric alcohol and trihydroxylic alcohol, the tetrahydroxylic alcohol of chain carry out esterification synthesizing polyester polyalcohol, successfully sulfonate groups can be connect
Enter the molecular backbone of PEPA, because sulfonate groups are a kind of polar hydrophilic groups, with sucting electronic effect, be conducive to
The infiltration of water, while having the regularity for changing polyester macromolecule segment, increases macromolecular state of aggregation loosening degree, these works
During with being all conducive to downstream to prepare waterborne polyurethane resin, solid content brings up to 60% from 30% or so；
(2) the fire-retardant sulphonate-base PEPA of Halogen copoly type of the invention, by using the dihydric alcohol containing side chain
Highly branched chain PEPA is synthesized as monomer with trihydroxylic alcohol, tetrahydroxylic alcohol, because of dihydric alcohol and trihydroxylic alcohol, tetrahydroxylic alcohol containing side chain
With T-shaped structure, the highly branched chain PEPA synthesized with it is with compared with the PEPA that straight dihydric alcohol is synthesized, having
There are more preferable permeability, wetability and hydrolytic resistance, general PEPA is stored 3 months, acid number bounce-back 10%, with the present invention
The fire-retardant sulphonate-base PEPA prepared is stored 6 months, and the bounce-back of its acid number is less than 3%.In addition, the dihydric alcohol containing side chain
Introducing with trihydroxylic alcohol, tetrahydroxylic alcohol increases the intermolecular distance of highly branched chain PEPA, there is destruction to make molecule regularity
With preventing the appearance of PEPA crystalline polamer.PEPA crystalline polamer is more serious, is preparing aqueous polyurethane coating
During glue, its glued membrane is harder, causes the fabric softness after coating to decline, and feel is deteriorated；
(3) the fire-retardant sulphonate-base PEPA of Halogen copoly type of the invention, by the way that the monomer containing ignition-proof element is drawn
Enter in PEPA backbone structure, it is fire-retardant after repeatedly being washed with fabric compared with outer addition fire retardant realizes fire-retardant purpose
Property do not decline, in the absence of fire retardant migrate phenomenon, it is achieved thereby that permanent fire retardant purpose；
(4) the fire-retardant sulphonate-base PEPA of Halogen copoly type of the invention, by method of fractional steps technique, will have hydrophilic
Property extremely strong monomer containing sulfonate groups and activated monomer with ignition-proof element introduce the host molecule chain structure of PEPA
In, to make the PEPA of preparation have water-soluble and anti-flammability dual-use function, it is to avoid prepares the resistance of high solids content (60%)
When firing waterborne polyurethane resin, it is respectively necessary for adding containing sulfonic PEPA and the PEPA containing anti-flammability, by
It is different in the viscosity, density, polarity of both PEPAs, it may appear that poor compatibility, uneven phenomenon is mixed, is being prepared
During aqueous polyurethane coating glue, glued membrane adhesiveness can be caused to be deteriorated, come off, coating layer thickness is uneven, and what anti-flammability had differences shows
As；Also fire retardant can be diluted, cause anti-flammability to decline, downstream producer to obtain qualified anti-flammability, it is necessary to add 3 more~
4% flame retardant polyester polyalcohol, causes cost to increase；
(5) the fire-retardant sulphonate-base PEPA of Halogen copoly type of the invention, it is adaptable to prepare halogen-free flameproof aqueous poly-
Urethane resin, can be widely applied to coating, adhesive, fabric coating and finishing agent, leather finishing agent, sheet surface treating agent etc.
Production and manufacture；
(6) technique of the fire-retardant sulphonate-base PEPA of the inventive method synthesis is simple, controllable, it is easy to industrial metaplasia
Contamination-free is produced in production, whole process, meets environmental requirement, and easily operation, practical.
Embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention
It is whole, still fall within protection scope of the present invention.
The preparation of Part I copoly type sulfonate
1st, basic technology：
By 1000 mass parts DMIP -5- sulfonate, 230~470 mass parts dihydric alcohols and 1.2~1.6
Mass parts of catalyst B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, the material of reactor A from room temperature to
140~150 DEG C start to distillate methanol, when liquid outlet quantity is seldom (reaction time is usually 2~3 hours), in control rectifying capital
Temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230~235 DEG C from 140~150 DEG C, (the reaction untill it can not go out liquid
Time is usually 3~4 hours), stop reaction, be finally cooled to less than 100 DEG C, both obtain copoly type sulfonate, it is standby；
2nd, raw material：
DMIP -5- sulfonate (hereinafter simply referred to as sulfonate)：A1 is DMIP -5- sulphurs
Sour sodium, A2 are that DMIP -5- potassium sulfonates, A3 are DMIP -5- Sulfonic Lithiums；
Dihydric alcohol：B1 is that ethylene glycol, B2 are that 1,6-HD, B3 are that 1,7- heptandiols, B4 are that 1,8- ethohexadiols, B5 are 1,
9- nonanediols, B6 are that 1,2- propane diols, B7 are that 1,2- butanediols, B8 are that 1,3 butylene glycol, B9 are that 1,2- pentanediols, B10 are new
Pentanediol；
Catalyst B：Lithium acetate, magnesium acetate, zinc acetate, sodium acetate, calcium acetate.
3rd, copoly type sulfonate is prepared
Embodiment 1-1：
To accurately it weigh, sulfonate is 1000 ㎏ A1, dihydric alcohol is 230 ㎏ B1, and catalyst B is 0.5 ㎏ lithium acetates and 0.8
㎏ magnesium acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stirs, since room temperature to distillating methanol 140 DEG C,
When liquid outlet quantity is seldom, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230 DEG C from 140 DEG C, directly
Untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, both obtain copoly type sulfonate 1-1, it is standby.
Embodiment 1-2：
To accurately weigh, sulfonate is 1000 ㎏ A2, dihydric alcohol is 416 ㎏ B2, catalyst B be 0.5 ㎏ B lithium acetates and
0.7 ㎏ zinc acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stirs, since room temperature to distillating first 142 DEG C
Alcohol, when liquid outlet quantity is seldom, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230 from 142 DEG C
DEG C, untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, both obtain copoly type sulfonate 1-2, it is standby.
Embodiment 1-3：
To accurately it weigh, sulfonate is 1000 ㎏ A3, dihydric alcohol is 299 ㎏ B6, and catalyst B is 0.6 ㎏ magnesium acetates and 0.6
㎏ zinc acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stirs, since room temperature to distillating methanol 145 DEG C,
When liquid outlet quantity is seldom, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230 DEG C from 145 DEG C, directly
Untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, both obtain copoly type sulfonate 1-3, it is standby.
Embodiment 1-4：
To accurately it weigh, sulfonate is 500 ㎏ A1 and 500 ㎏ A2, dihydric alcohol is 147 ㎏ B1 and 147 ㎏ B2, catalyst B
Be 0.7 ㎏ sodium acetates and 0.6 ㎏ zinc acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stir, from room temperature to
140 DEG C start to distillate methanol, when liquid outlet quantity is seldom, and in control rectifying capital, temperature is no more than in the case of 65 DEG C, then from 140 DEG C
230 DEG C are to slowly warm up to, untill it can not go out liquid, stops reaction, is finally cooled to less than 100 DEG C, both obtain copoly type sulfonic acid
Salt 1-4, it is standby.
Embodiment 1-5：
To accurately it weigh, sulfonate is 500 ㎏ A1 and 500 ㎏ A3, dihydric alcohol is 205 ㎏ B3 and B7 205 ㎏, catalyst B
Be 0.7 ㎏ sodium acetates and 0.8 ㎏ calcium acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stir, from room temperature to
145 DEG C start to distillate methanol, when liquid outlet quantity is seldom, and in control rectifying capital, temperature is no more than in the case of 65 DEG C, then from 145 DEG C
230 DEG C are to slowly warm up to, untill it can not go out liquid, stops reaction, is finally cooled to less than 100 DEG C, both obtain copoly type sulfonic acid
Salt 1-5, it is standby.
Embodiment 1-6：
To accurately it weigh, sulfonate is 500 ㎏ A2 and 500 ㎏ A3, dihydric alcohol is 235 ㎏ B5 and 235 ㎏ B10, catalyst B
Be 0.8 ㎏ zinc acetates and 0.8 ㎏ calcium acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stir, from room temperature to
150 DEG C start to distillate methanol, when liquid outlet quantity is seldom, and in control rectifying capital, temperature is no more than in the case of 65 DEG C, then from 150 DEG C
235 DEG C are to slowly warm up to, untill it can not go out liquid, stops reaction, is finally cooled to less than 100 DEG C, both obtain copoly type sulfonic acid
Salt 1-6, it is standby.
Embodiment 1-7：
To accurately it weigh, sulfonate is 667 ㎏ A1 and 333 ㎏ A, dihydric alcohol is 294 ㎏ B4 and 147 ㎏ B8, and catalyst B is
0.7 ㎏ magnesium acetates and 0.6 ㎏ calcium acetates, input have in the reactor A of rectifying column, be passed through nitrogen, stir, from room temperature to
150 DEG C start to distillate methanol, when liquid outlet quantity is seldom, and in control rectifying capital, temperature is no more than in the case of 65 DEG C, then from 150 DEG C
235 DEG C are to slowly warm up to, untill it can not go out liquid, stops reaction, is finally cooled to less than 100 DEG C, both obtain copoly type sulfonic acid
Salt 1-7, it is standby.
Embodiment 1-8：
To accurately it weigh, sulfonate is 333 ㎏ A1 and 667 ㎏ A3, dihydric alcohol is 111 ㎏ B1,55 ㎏ B2 and 166 ㎏ B10,
Catalyst B is 0.5 ㎏ lithium acetates, 0.4 ㎏ magnesium acetates and 0.7 ㎏ sodium acetates, and input has in the reactor A of rectifying column, is passed through nitrogen
Gas, stirring, since room temperature to methanol is distillated 147 DEG C, when liquid outlet quantity is seldom, in control rectifying capital temperature no more than 65
In the case of DEG C, then from 147 DEG C 235 DEG C are to slowly warm up to, untill it can not go out liquid, stop reaction, be finally cooled to 100 DEG C
Hereinafter, both copoly type sulfonate 1-8, it is standby.
Embodiment 1-9：
To accurately it weigh, sulfonate is 600 ㎏ A2,400 ㎏ A3, dihydric alcohol is 93 ㎏ B3,185 ㎏ B5 and 139 ㎏ B6, is urged
Agent B is 0.5 ㎏ calcium acetates, 0.4 ㎏ magnesium acetates and 0.7 ㎏ sodium acetates, and input has in the reactor A of rectifying column, is passed through nitrogen,
Stirring, since room temperature to methanol is distillated 150 DEG C, when liquid outlet quantity is seldom, in control rectifying capital temperature no more than 65 DEG C
In the case of, then from 150 DEG C be to slowly warm up to 235 DEG C, untill it can not go out liquid, stop reaction, be finally cooled to 100 DEG C with
Under, both copoly type sulfonate 1-9, it is standby.
Embodiment 1-10：
To accurately weigh, sulfonate is 334 ㎏ A1,333 ㎏ A2 and 333 ㎏ A3, dihydric alcohol be 53 ㎏ B4,212 ㎏ B7 and
106 ㎏ B9, catalyst B are 0.5 ㎏ calcium acetates, 0.4 ㎏ magnesium acetates and 0.6 ㎏ zinc acetates, and input has the reactor A of rectifying column
In, nitrogen is passed through, is stirred, since room temperature to methanol is distillated 150 DEG C, when liquid outlet quantity is seldom, in control rectifying capital
Temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 235 DEG C from 150 DEG C, untill it can not go out liquid, stops reaction, finally
Be cooled to less than 100 DEG C, both copoly type sulfonate 1-10, it is standby.
Embodiment 1-11：
To accurately weigh, sulfonate is 250 ㎏ A1,500 ㎏ A2 and 250 ㎏ A3, dihydric alcohol be 53 ㎏ B3,106 ㎏ B5,
159 ㎏ B6 and 53 ㎏ B10, catalyst B are 0.3 ㎏ lithium acetates, 0.5 ㎏ calcium acetates, 0.4 ㎏ magnesium acetates and 0.4 ㎏ zinc acetates, throwing
Enter to have in the reactor A of rectifying column, be passed through nitrogen, stir, since room temperature to distillating methanol 140 DEG C, when liquid outlet quantity very
When few, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230 DEG C from 140 DEG C, until that can not go out liquid
Untill, stop reaction, be finally cooled to less than 100 DEG C, both obtain copoly type sulfonate 1-11, it is standby.
Embodiment 1-12：
To accurately it weigh, sulfonate is 500 ㎏ A1,167 ㎏ A2 and 333 ㎏ A3, dihydric alcohol is 45 ㎏ B1,90 ㎏ B3,90
㎏ B5,45 ㎏ B7 and 135 ㎏ B9, catalyst B are 0.2 ㎏ lithium acetates, 0.4 ㎏ magnesium acetates, 0.3 ㎏ zinc acetates, 0.4 ㎏ sodium acetates
With 0.3 ㎏ calcium acetates, input has in the reactor A of rectifying column, is passed through nitrogen, stirs, since room temperature to distillating 148 DEG C
Methanol, when liquid outlet quantity is seldom, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 235 from 148 DEG C
DEG C, untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, both obtain copoly type sulfonate 1-12, it is standby.
The preparation of the fire-retardant sulphonate-base PEPA of Part II Halogen copoly type
1st, basic technology：
Weigh 25.92~43.20 mass parts copoly type sulfonate, 443.66~552.18 mass parts binary of fatty acids,
292.56~423.06 mass parts polyalcohols, 119.99~154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants, 0.60~
1.06 mass parts of catalyst A；
Each raw material and consumption described in composition of raw materials by the fire-retardant sulphonate-base PEPA synthesis of Halogen copoly type, throw
Enter to having in the reactor B of rectifying column, be passed through nitrogen, stir, the material of reactor B is from room temperature, when temperature in reactor B
110~120 DEG C (temperature 1) are reached by room temperature, when starting to distillate water, the insulation reaction time is 2~3 hours (soaking time A), instead
When control rectifying column head temperature remains at 80~105 DEG C (temperature 2) during answering, when rectifying column head temperature is reduced to 75
When below DEG C, then slow temperature is when reaching 160 DEG C, continues insulation reaction 1 hour, when being then slowly warming up to 180 DEG C, continues to protect
After temperature reaction 3~4 hours (soaking time B), then when being slowly warming up to 200 DEG C, continue 2~3 hours (soaking times of insulation reaction
C), then slowly it is warming up to 230~240 DEG C (temperature 3), continues insulation reaction 2~3 hours (soaking time D), when anti-during reaction
The control of material acid number is answered in≤15mgKOH/g, and the rectifying column head temperature of reactor B is when being down to less than 75 DEG C, stops heating,
Reaction mass is incubated when being down to 220 DEG C, and slow suction is to -0.090~-0.095MPa, as acid number≤2mgKOH/
During g, stop reaction, cooling is made the fire-retardant sulphonate-base PEPA of Halogen copoly type；
2nd, raw material：
Copoly type sulfonate：Prepared by specific embodiment Part I copoly type sulfonate, D1 is copoly type sulfonate 1-
1st, D2 is that copoly type sulfonate 1-2, D3 are that copoly type sulfonate 1-3, D4 are that copoly type sulfonate 1-4, D5 are copoly type sulfonic acid
Salt 1-5, D6 are that copoly type sulfonate 1-6, D7 are that copoly type sulfonate 1-7, D8 are that copoly type sulfonate 1-8, D9 are copoly types
Sulfonate 1-9, D10 are that copoly type sulfonate 1-10, D11 are that copoly type sulfonate 1-11, D12 are copoly type sulfonate 1-12；
Binary of fatty acids：C1 is that succinic acid, C2 are that glutaric acid, C3 are that adipic acid, C4 are that azelaic acid, C5 are SAs；
Polyalcohol：B6 is that 1,2- propane diols, B8 are that 1,3 butylene glycol, B9 are that 1,2 pentanediols, E1 are that glycerine, E2 are three
Hydroxymethyl-propane, E3 are pentaerythrites；
Halogen-free phosphorus-containing copoly type fire retardant：F1 is that hydroxymethyl phenyl hypophosphorous acid, F2 are that ethoxy phenyl hypophosphorous acid, F3 are hydroxyls
Propyl group phenyl hypophosphorous acid, F4 are carboxyethyl phenyl hypophosphorous acid；
Catalyst A：Tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate, stannous chloride.
3rd, the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared
Table one：Embodiment 2-1~2-12 prepare the raw material of the fire-retardant sulphonate-base PEPA of Halogen copoly type, consumption and
Process parameter table (unit：㎏, DEG C, h, following ratio be mass ratio)
Note：The corresponding mol ratios of ※ 1 are 50:50:5, ※ 2 corresponding mol ratios are 50:50:15, ※ 3 corresponding mol ratios
It is 50:50:8, ※ 4 corresponding mol ratios are 100:5:5:5, ※ 5 corresponding mol ratios are 40:30:30:5:3:2.
Table two：The quality technology that embodiment 2-1~2-12 prepares the fire-retardant sulphonate-base PEPA of Halogen copoly type refers to
Mark table
Embodiment 3：
A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, by 25.92 mass parts copoly type sulfonate, 443.66
Mass parts binary of fatty acids, 292.56 mass parts polyalcohols, 119.99 mass parts halogen-free phosphorus-containing copoly type fire retardants and 0.60
Mass parts of catalyst A is mixed, and through esterification and removes moisture, then through polycondensation, the obtained fire-retardant sulphonate-base of Halogen copoly type
PEPA.
Embodiment 4：
A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, by 43.20 mass parts copoly type sulfonate, 552.18
Mass parts binary of fatty acids, 423.06 mass parts polyalcohols, 154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants and 1.06
Mass parts of catalyst A is mixed, and through esterification and removes moisture, then through polycondensation, the obtained fire-retardant sulphonate-base of Halogen copoly type
PEPA.
Embodiment 5：
A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, by 34.56 mass parts copoly type sulfonate, 497.92
Mass parts binary of fatty acids, 357.81 mass parts polyalcohols, 137.14 mass parts halogen-free phosphorus-containing copoly type fire retardants and 0.83
Mass parts of catalyst A is mixed, and through esterification and removes moisture, then through polycondensation, the obtained fire-retardant sulphonate-base of Halogen copoly type
PEPA.
Embodiment 6~12：
A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, by 25.92~43.20 mass parts copoly type sulfonic acid
Salt, 443.66~552.18 mass parts binary of fatty acids, 292.56~423.06 mass parts polyalcohols, 119.99~154.29 matter
Part halogen-free phosphorus-containing copoly type fire retardant and 0.60~1.06 mass parts of catalyst A mixing are measured, through esterification and water is removed
Point, then through polycondensation, the obtained fire-retardant sulphonate-base PEPA of Halogen copoly type；Each component raw material in embodiment 6~12
The specific mass parts consumption (unit of mass parts：Gram) see the table below：
In above-described embodiment 3~12：The copoly type sulfonate can be the compound for having following general structure：
In formula：Me is chemical element Na, K or Li, R1For C2-9H4-18Alkylidene, R2For C2-9H4-18Alkylidene, and
R in same molecule1With R2Relation is：R1=R2Or R1≠R2；I.e.：Can be R in same molecule1=R2=-CH2CH2-, or：
R1=-CH2CH2- and
In above-described embodiment 3~12：The binary of fatty acids can for succinic acid, glutaric acid, adipic acid, azelaic acid, with
And mixture more than one or both of SA, preferred adipic acid；
In above-described embodiment 3~12：The polyalcohol can be one in 1,2- propane diols, 1,3 butylene glycol, 1,2 pentanediols
Kind is two or more, and 1,2-PD, 1,3-BDO, 1, one or more kinds of and glycerine, three hydroxyls in 2 pentanediols
One or more kinds of mixture in methylpropane, pentaerythrite；
In the polyalcohol, the mol ratio of glycol and triol, tetrol or triol+tetrol can be：Glycol：(triol, tetrol
Or triol+tetrol)=100：5~15, mol ratio preferably is 100：5~8.
In above-described embodiment 3~12：The halogen-free phosphorus-containing copoly type fire retardant can be hydroxymethyl phenyl hypophosphorous acid, hydroxyl second
Mixture more than one or both of base phenyl hypophosphorous acid, hydroxypropyl phenyl hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
In above-described embodiment 3~12：The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, di lauric dibutyl
Any of tin, stannous octoate and stannous chloride etc. or two or more mixtures；
In above-described embodiment 3~12：The average functionality of the fire-retardant sulphonate-base PEPA of Halogen copoly type is
2.0th, viscosity be at 25 DEG C≤10000mPaS, 55~65mgKOH/g of hydroxyl value, acid number be≤2mgKOH/g, and in 25 DEG C of normal temperature
Under the conditions of storage 6 months without hydrolysis phenomena.
In above-described embodiment 3~12：The copoly type sulfonate can be prepared with following method：By between 1000 mass parts
Rutgers -5- sulfonate, 230 mass parts dihydric alcohols and 1.2 mass parts of catalyst B inputs have the reactor of rectifying column
In A, be passed through nitrogen, stir, the material of reactor A since room temperature to methanol is distillated 140 DEG C, it is seldom when distillating liquid measure
When, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 230 DEG C from 140 DEG C, is until that can not go out liquid
Only, stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made；
DMIP -5- the sulfonate can be Sodium Dimethyl Isophthalate-5-sulfonate, isophthalic diformazan
One or more kinds of mixture in dimethyl phthalate -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums, preferably
Sodium Dimethyl Isophthalate-5-sulfonate；
The dihydric alcohol can be ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,
One or more kinds of mixing in 2- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol
Thing；
The catalyst B can be acetate class compound, be lithium acetate, magnesium acetate, zinc acetate, sodium acetate and vinegar
One or more kinds of mixture in sour calcium.
In above-described embodiment 3~12：The copoly type sulfonate can be prepared with following method：By between 1000 mass parts
Rutgers -5- sulfonate, 470 mass parts dihydric alcohols and 1.6 mass parts of catalyst B inputs have the reactor of rectifying column
In A, be passed through nitrogen, stir, the material of reactor A since room temperature to methanol is distillated 150 DEG C, it is seldom when distillating liquid measure
When, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 235 DEG C from 150 DEG C, is until that can not go out liquid
Only, stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made；
DMIP -5- the sulfonate can be Sodium Dimethyl Isophthalate-5-sulfonate, isophthalic diformazan
One or more kinds of mixture in dimethyl phthalate -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums, preferably
Sodium Dimethyl Isophthalate-5-sulfonate；
The dihydric alcohol can be ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,
One or more kinds of mixing in 2- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol
Thing；
The catalyst B can be acetate class compound, be lithium acetate, magnesium acetate, zinc acetate, sodium acetate and vinegar
One or more kinds of mixture in sour calcium.
In above-described embodiment 3~12：The copoly type sulfonate can be prepared with following method：By between 1000 mass parts
Rutgers -5- sulfonate, 350 mass parts dihydric alcohols and 1.4 mass parts of catalyst B inputs have the reactor of rectifying column
In A, be passed through nitrogen, stir, the material of reactor A since room temperature to methanol is distillated 145 DEG C, it is seldom when distillating liquid measure
When, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is to slowly warm up to 233 DEG C from 1450 DEG C, until that can not go out liquid
Untill, stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made；
DMIP -5- the sulfonate can be Sodium Dimethyl Isophthalate-5-sulfonate, isophthalic diformazan
One or more kinds of mixture in dimethyl phthalate -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums, preferably
Sodium Dimethyl Isophthalate-5-sulfonate；
The dihydric alcohol can be ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,
One or more kinds of mixing in 2- propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol
Thing；
The catalyst B can be acetate class compound, be lithium acetate, magnesium acetate, zinc acetate, sodium acetate and vinegar
One or more kinds of mixture in sour calcium.
Embodiment 13：
A kind of preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type, step is as follows：
A, prepare copoly type sulfonate：
By the catalysis of 1000 mass parts DMIP -5- sulfonate, 230 mass parts dihydric alcohols and 1.2 mass parts
Agent B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, and the material of reactor A is since room temperature to evaporating 140 DEG C
Go out methanol, when distillate liquid measure it is seldom when, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is slowly heated up from 140 DEG C
To 230 DEG C, untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made, it is standby
With；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid two
One or more kinds of mixtures, preferably isophthalic in methyl esters -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums
Dicarboxylic acid dimethyl ester -5- sodium sulfonates；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- third
One or more kinds of mixture in glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is acetic acid salt compounds, is lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
One or more kinds of mixture in；
B, prepare the fire-retardant sulphonate-base PEPA of Halogen copoly type：
(a) feed proportioning：
Weigh the mass parts copoly type sulfonate of raw material 25.92,443.66 mass parts binary of fatty acids, 292.56 mass parts many
First alcohol, 119.99 mass parts halogen-free phosphorus-containing copoly type fire retardants, 0.60 mass parts of catalyst A, it is standby；
The copoly type sulfonate is produced by step a；
The binary of fatty acids is any of succinic acid, glutaric acid, adipic acid, azelaic acid and SA or two
Plant the mixture of the above；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2-
In propane diols, 1,3 butylene glycol, 1,2 pentanediols one in one or more kinds of and glycerine, trimethylolpropane, pentaerythrite
Plant or two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl benzene
Mixture more than one or both of base hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and chlorine
Change any of stannous etc. or two or more mixtures；
(b) the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared：
By each raw material and consumption described in step (a) feed proportioning, put into the reactor B of rectifying column, be passed through nitrogen,
Stirring, the material of reactor B, when temperature reaches 110 DEG C by room temperature in reactor B, when starting to distillate water, is protected from room temperature
The warm reaction time is 3 hours, when control rectifying column head temperature remains at 80 DEG C during reaction, when rectifying column head temperature
When being reduced to less than 75 DEG C, then (slow) rise temperature reaches 160 DEG C, continues insulation reaction 1 hour, is then slowly warming up to
180 DEG C, continue insulation reaction after 3 hours, then be slowly warming up to 200 DEG C, continue insulation reaction 2 hours, then be slowly warming up to 230
DEG C, continue insulation reaction 3 hours, when the control of reaction mass acid number is in≤15mgKOH/g during reaction, and the rectifying of reactor B
When column top temperature is down to less than 75 DEG C, stops heating, be incubated when reaction mass is down into 220 DEG C, and slowly vacuumize
Degree is to -0.090~-0.095MPa, as acid number≤2mgKOH/g, stops reaction, and cooling is made the fire-retardant sulphur of Halogen copoly type
Hydrochlorate base PEPA.
Embodiment 14：
A kind of preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type, step is as follows：
A, prepare copoly type sulfonate：
By the catalysis of 1000 mass parts DMIP -5- sulfonate, 470 mass parts dihydric alcohols and 1.6 mass parts
Agent B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, and the material of reactor A is since room temperature to evaporating 150 DEG C
Go out methanol, when distillate liquid measure it is seldom when, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is slowly heated up from 150 DEG C
To 235 DEG C, untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made, it is standby
With；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid two
One or more kinds of mixtures, preferably isophthalic in methyl esters -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums
Dicarboxylic acid dimethyl ester -5- sodium sulfonates；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- third
One or more kinds of mixture in glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is acetic acid salt compounds, is lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
One or more kinds of mixture in；
B, prepare the fire-retardant sulphonate-base PEPA of Halogen copoly type：
(a) feed proportioning：
Weigh the mass parts copoly type sulfonate of raw material 43.20,552.18 mass parts binary of fatty acids, 423.06 mass parts many
First alcohol, 154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants, 1.06 mass parts of catalyst A, it is standby；
The copoly type sulfonate is produced by step a；
The binary of fatty acids is any of succinic acid, glutaric acid, adipic acid, azelaic acid and SA or two
Plant the mixture of the above；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2-
In propane diols, 1,3 butylene glycol, 1,2 pentanediols one in one or more kinds of and glycerine, trimethylolpropane, pentaerythrite
Plant or two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl benzene
Mixture more than one or both of base hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and chlorine
Change any of stannous etc. or two or more mixtures；
(b) the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared：
By each raw material and consumption described in step (a) feed proportioning, put into the reactor B of rectifying column, be passed through nitrogen,
Stirring, the material of reactor B, when temperature reaches 120 DEG C by room temperature in reactor B, when starting to distillate water, is protected from room temperature
The warm reaction time is 2 hours, when control rectifying column head temperature remains at 105 DEG C during reaction, the temperature at the top of rectifying column
When degree is reduced to less than 75 DEG C, then (slow) rise temperature reaches 160 DEG C, continues insulation reaction 1 hour, is then slowly warming up to
180 DEG C, continue insulation reaction after 4 hours, then be slowly warming up to 200 DEG C, continue insulation reaction 3 hours, then be slowly warming up to 240
DEG C, continue insulation reaction 2 hours, when the control of reaction mass acid number is in≤15mgKOH/g during reaction, and the rectifying of reactor B
When column top temperature is down to less than 75 DEG C, stops heating, be incubated when reaction mass is down into 220 DEG C, and slowly vacuumize
Degree is to -0.090~-0.095MPa, as acid number≤2mgKOH/g, stops reaction, and cooling is made the fire-retardant sulphur of Halogen copoly type
Hydrochlorate base PEPA.
Embodiment 15：
A kind of preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type, step is as follows：
A, prepare copoly type sulfonate：
By the catalysis of 1000 mass parts DMIP -5- sulfonate, 350 mass parts dihydric alcohols and 1.4 mass parts
Agent B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, and the material of reactor A is since room temperature to evaporating 145 DEG C
Go out methanol, when distillate liquid measure it is seldom when, in control rectifying capital, temperature is no more than in the case of 65 DEG C, then is slowly heated up from 145 DEG C
To 234 DEG C, untill it can not go out liquid, stop reaction, be finally cooled to less than 100 DEG C, that is, copoly type sulfonate is made, it is standby
With；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid two
One or more kinds of mixtures, preferably isophthalic in methyl esters -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums
Dicarboxylic acid dimethyl ester -5- sodium sulfonates；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- third
One or more kinds of mixture in glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is acetic acid salt compounds, is lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
One or more kinds of mixture in；
B, prepare the fire-retardant sulphonate-base PEPA of Halogen copoly type：
(a) feed proportioning：
Weigh the mass parts copoly type sulfonate of raw material 34.56,497.92 mass parts binary of fatty acids, 357.81 mass parts many
First alcohol, 137.14 mass parts halogen-free phosphorus-containing copoly type fire retardants and 0.83 mass parts of catalyst A, it is standby；
The copoly type sulfonate is produced by step a；
The binary of fatty acids is any of succinic acid, glutaric acid, adipic acid, azelaic acid and SA or two
Plant the mixture of the above；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2-
In propane diols, 1,3 butylene glycol, 1,2 pentanediols one in one or more kinds of and glycerine, trimethylolpropane, pentaerythrite
Plant or two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl benzene
Mixture more than one or both of base hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and chlorine
Change any of stannous etc. or two or more mixtures；
(b) the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared：
By each raw material and consumption described in step (a) feed proportioning, put into the reactor B of rectifying column, be passed through nitrogen,
Stirring, the material of reactor B, when temperature reaches 115 DEG C by room temperature in reactor B, when starting to distillate water, is protected from room temperature
The warm reaction time is 2.5 hours, when control rectifying column head temperature remains at 95 DEG C during reaction, the temperature at the top of rectifying column
When degree is reduced to less than 75 DEG C, then (slow) rise temperature reaches 160 DEG C, continues insulation reaction 1 hour, is then slowly warming up to
180 DEG C, continue insulation reaction after 3.5 hours, then be slowly warming up to 200 DEG C, continue insulation reaction 2.5 hours, then slow heating
To 235 DEG C, continue insulation reaction 2.5 hours, when the control of reaction mass acid number is in≤15mgKOH/g during reaction, and reactor B
Rectifying column head temperature when being down to less than 75 DEG C, stop heating, be incubated when reaction mass is down into 220 DEG C, and slowly
Suction is to -0.090~-0.095MPa, as acid number≤2mgKOH/g, stops reaction, and cooling is made Halogen copoly type
Fire-retardant sulphonate-base PEPA.
Embodiment 16~22：
A kind of preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type, step is as follows：
A, prepare copoly type sulfonate：
By 1000 mass parts DMIP -5- sulfonate, 230~470 mass parts dihydric alcohols and 1.2~1.6
Mass parts of catalyst B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, the material of reactor A from room temperature to
140~150 DEG C start to distillate methanol, when distillate liquid measure it is seldom when, in the case where control rectifying capital temperature is no more than 65 DEG C, then
Be to slowly warm up to 230~235 DEG C from 140~150 DEG C, untill it can not go out liquid, stop reaction, be finally cooled to 100 DEG C with
Under, that is, copoly type sulfonate is made, it is standby；
The specific mass parts consumption (unit of mass parts of each component raw material in embodiment 16~22：Gram) see the table below：
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid two
One or more kinds of mixtures, preferably isophthalic in methyl esters -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums
Dicarboxylic acid dimethyl ester -5- sodium sulfonates；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- third
One or more kinds of mixture in glycol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is acetic acid salt compounds, is lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
One or more kinds of mixture in；
B, prepare the fire-retardant sulphonate-base PEPA of Halogen copoly type：
(a) feed proportioning：
Weigh the mass parts copoly type sulfonate of raw material 25.92~43.20,443.66~552.18 mass parts di-fatties
Acid, 292.56~423.06 mass parts polyalcohols, 119.99~154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants, 0.60~
1.06 mass parts of catalyst A, it is standby；The specific mass parts consumption (unit of mass parts of each component raw material in embodiment 16~22：
Gram) any in be the same as Example 6~12, omit；
The copoly type sulfonate is produced by step a；
The binary of fatty acids is any of succinic acid, glutaric acid, adipic acid, azelaic acid and SA or two
Plant the mixture of the above；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2-
In propane diols, 1,3 butylene glycol, 1,2 pentanediols one in one or more kinds of and glycerine, trimethylolpropane, pentaerythrite
Plant or two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl benzene
Mixture more than one or both of base hypophosphorous acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and chlorine
Change any of stannous etc. or two or more mixtures；
(b) the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared：
By each raw material and consumption described in step (a) feed proportioning, put into the reactor B of rectifying column, be passed through nitrogen,
Stirring, the material of reactor B is from room temperature, when temperature reaches 110~120 DEG C by room temperature in reactor B, when starting to distillate water
Rise, the insulation reaction time is 2~3 hours, when control rectifying column head temperature remains at 80~105 DEG C during reaction, when
When rectifying column head temperature is reduced to less than 75 DEG C, then (slow) rise temperature reaches 160 DEG C, continues insulation reaction 1 hour, so
Slowly be warming up to 180 DEG C afterwards, continue insulation reaction after 3~4 hours, then be slowly warming up to 200 DEG C, to continue insulation reaction 2~3 small
When, then be slowly warming up to 230~240 DEG C, continue insulation reaction 2~3 hours, during reaction when the control of reaction mass acid number≤
15mgKOH/g, and the rectifying column head temperature of reactor B is when being down to less than 75 DEG C, stops heating, reaction mass is down into 220
DEG C when be incubated, and slow suction is to -0.090~-0.095MPa, as acid number≤2mgKOH/g, stops reaction, cold
But, that is, the fire-retardant sulphonate-base PEPA of Halogen copoly type is made.
In above-described embodiment 13~22：In the polyalcohol, the mol ratio of glycol and triol, tetrol or triol+tetrol can
Think：Glycol：(triol, tetrol or triol+tetrol)=100：5~15, mol ratio preferably is 100：5~8.
In above-described embodiment 13~22：The copoly type sulfonate can be the copoly type sulfonic acid for having following general structure
Salt：
In formula：Me is chemical element Na, K or Li, R1For C2-9H4-18Alkylidene, R2For C2-9H4-18Alkylidene, and
R in same molecule1With R2Relation is：R1=R2Or R1≠R2；I.e.：Can be R in same molecule1=R2=-CH2CH2-, or R1
=-CH2CH2- and
The average functionality of the fire-retardant sulphonate-base PEPA of Halogen copoly type is made described in above-described embodiment 13~22
Be at 25 DEG C for 2.0, viscosity≤10000mPaS, 55~65mgKOH/g of hydroxyl value, acid number be≤2mgKOH/g, and in normal temperature 25
6 months are stored under the conditions of DEG C without hydrolysis phenomena.
In above-described embodiment：It is especially not dated in the percentage used, be quality (weight) percentage or
Well known to a person skilled in the art percentage；In the ratio used, do not indicate especially, be quality (weight) ratio；
The parts by weight can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, pressure etc.) and each component numerical quantity in each step etc. are
Scope, any point is applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology, and the raw material are
Commercially available prod.
It can implement the invention is not restricted to above-described embodiment, described in present invention and with the good result.
Claims (8)
1. a kind of fire-retardant sulphonate-base PEPA of Halogen copoly type, it is characterized in that：By 25.92~43.20 mass parts copolymerization
Type sulfonate, 443.66~552.18 mass parts binary of fatty acids, 292.56~423.06 mass parts polyalcohols, 119.99~
154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants and 0.60~1.06 mass parts of catalyst A mixing, through esterification simultaneously
Moisture is removed, then through polycondensation, the obtained fire-retardant sulphonate-base PEPA of Halogen copoly type；
The copoly type sulfonate has following general structure：
In formula：Me is chemical element Na, K or Li, R1For C2-9H4-18Alkylidene, R2For C2-9H4-18Alkylidene；
The binary of fatty acids is more than one or both of succinic acid, glutaric acid, adipic acid, azelaic acid and SA
Mixture；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2- the third two
In alcohol, 1,3 butylene glycol, 1,2 pentanediols it is one or more kinds of with it is a kind of in glycerine, trimethylolpropane, pentaerythrite or
Two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl phenyl
Mixture more than one or both of phosphoric acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and protochloride
Any of tin or two or more mixtures.
2. the fire-retardant sulphonate-base PEPA of Halogen copoly type as described in claim 1, it is characterized in that：The polyalcohol
In, the mol ratio of glycol and triol, tetrol or triol+tetrol is：Glycol：(triol, tetrol or triol+tetrol)=100：5~
15。
3. the fire-retardant sulphonate-base PEPA of Halogen copoly type as described in claim 1, it is characterized in that：The Halogen copolymerization
The average functionality of the fire-retardant sulphonate-base PEPA of type be 2.0, viscosity be at 25 DEG C≤10000mPaS, hydroxyl value 55~
65mgKOH/g, acid number are≤2mgKOH/g, and under the conditions of 25 DEG C of normal temperature storage 6 months without hydrolysis phenomena.
4. the fire-retardant sulphonate-base PEPA of Halogen copoly type as described in claim 1, it is characterized in that：The copoly type sulphur
Hydrochlorate is prepared with following method：By 1000 mass parts DMIP -5- sulfonate, 230~470 mass parts binary
Alcohol and 1.2~1.6 mass parts of catalyst B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, the material of reactor A
Since room temperature to distillating methanol 140~150 DEG C, when distillate liquid measure it is seldom when, in control rectifying capital temperature no more than 65
In the case of DEG C, then from 140~150 DEG C 230~235 DEG C are to slowly warm up to, untill it can not go out liquid, stop reaction, finally
Less than 100 DEG C are cooled to, that is, copoly type sulfonate is made；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid diformazan
One or more kinds of mixture in ester -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- the third two
One or more kinds of mixture in alcohol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is mixing one or more kinds of in lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
Thing.
5. a kind of preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type, it is characterized in that step is as follows：
A, prepare copoly type sulfonate：
By 1000 mass parts DMIP -5- sulfonate, 230~470 mass parts dihydric alcohols and 1.2~1.6 mass
Part catalyst B inputs have in the reactor A of rectifying column, are passed through nitrogen, stir, the material of reactor A from room temperature to 140~
150 DEG C start to distillate methanol, when distillate liquid measure it is seldom when, in the case where control rectifying capital temperature is no more than 65 DEG C, then from 140
~150 DEG C are to slowly warm up to 230~235 DEG C, untill it can not go out liquid, stop reaction, are finally cooled to less than 100 DEG C, i.e.,
Copoly type sulfonate is made, it is standby；
DMIP -5- the sulfonate is Sodium Dimethyl Isophthalate-5-sulfonate, M-phthalic acid diformazan
One or more kinds of mixture in ester -5- potassium sulfonates and DMIP -5- Sulfonic Lithiums；
The dihydric alcohol is ethylene glycol, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,2- the third two
One or more kinds of mixture in alcohol, 1,2- butanediols, 1,3 butylene glycol, 1,2- pentanediols and neopentyl glycol；
The catalyst B is mixing one or more kinds of in lithium acetate, magnesium acetate, zinc acetate, sodium acetate and calcium acetate
Thing；
B, prepare the fire-retardant sulphonate-base PEPA of Halogen copoly type：
(a) feed proportioning：
Weigh the mass parts copoly type sulfonate of raw material 25.92~43.20,443.66~552.18 mass parts binary of fatty acids,
292.56~423.06 mass parts polyalcohols, 119.99~154.29 mass parts halogen-free phosphorus-containing copoly type fire retardants, 0.60~
1.06 mass parts of catalyst A, it is standby；
The copoly type sulfonate is produced by step a；
The binary of fatty acids be any of succinic acid, glutaric acid, adipic acid, azelaic acid and SA or two kinds with
On mixture；
The polyalcohol is 1,2-PD, 1,3-BDO, 1, one or more kinds of in 2 pentanediols, and 1,2- the third two
In alcohol, 1,3 butylene glycol, 1,2 pentanediols it is one or more kinds of with it is a kind of in glycerine, trimethylolpropane, pentaerythrite or
Two or more mixtures；
The halogen-free phosphorus-containing copoly type fire retardant is hydroxymethyl phenyl hypophosphorous acid, ethoxy phenyl hypophosphorous acid, hydroxypropyl phenyl
Mixture more than one or both of phosphoric acid and carboxyethyl phenyl hypophosphorous acid；
The catalyst A is tetrabutyl titanate, tetraisopropyl titanate, dibutyl tin laurate, stannous octoate and protochloride
Any of tin or two or more mixtures；
(b) the fire-retardant sulphonate-base PEPA of Halogen copoly type is prepared：
By each raw material and consumption described in step (a) feed proportioning, put into the reactor B of rectifying column, be passed through nitrogen, stir
Mix, the material of reactor B is from room temperature, when temperature reaches 110~120 DEG C by room temperature in reactor B, when starting to distillate water
Rise, the insulation reaction time is 2~3 hours, when control rectifying column head temperature remains at 80~105 DEG C during reaction, when
When rectifying column head temperature is reduced to less than 75 DEG C, then raises temperature and reach 160 DEG C, continue insulation reaction 1 hour, then slowly
It is warming up to 180 DEG C, continues insulation reaction after 3~4 hours, then is slowly warming up to 200 DEG C, continues insulation reaction 2~3 hours, then
It is slow to be warming up to 230~240 DEG C, continue insulation reaction 2~3 hours, during reaction when the control of reaction mass acid number≤
15mgKOH/g, and the rectifying column head temperature of reactor B is when being down to less than 75 DEG C, stops heating, reaction mass is down into 220
DEG C when be incubated, and slow suction is to -0.090~-0.095MPa, as acid number≤2mgKOH/g, stops reaction, cold
But, that is, the fire-retardant sulphonate-base PEPA of Halogen copoly type is made.
6. the preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type as described in claim 5, it is characterized in that：Institute
State in polyalcohol, the mol ratio of glycol and triol, tetrol or triol+tetrol is：Glycol：(triol, tetrol or triol+tetrol)=
100：5~15, mol ratio preferably is 100：5~8.
7. the preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type as described in claim 5, it is characterized in that：Institute
The average functionality for stating the fire-retardant sulphonate-base PEPA of obtained Halogen copoly type be 2.0, viscosity be at 25 DEG C≤
10000mPaS, 55~65mgKOH/g of hydroxyl value, acid number are≤2mgKOH/g, and store 6 months nothings under the conditions of 25 DEG C of normal temperature
Hydrolysis phenomena.
8. the preparation method of the fire-retardant sulphonate-base PEPA of Halogen copoly type as described in claim 5, it is characterized in that：Institute
It is the copoly type sulfonate for having following general structure to state copoly type sulfonate：
In formula：Me is chemical element Na, K or Li, R1For C2-9H4-18Alkylidene, R2For C2-9H4-18Alkylidene.
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| CN109503434A (en) * | 2018-11-16 | 2019-03-22 | 泰山医学院 | A kind of multicomponent process for catalytic synthesis of the modifying agent M-phthalic acid dipropylene glycol ester -5- sodium sulfonate of polyester PTT |
| CN109535041A (en) * | 2018-11-22 | 2019-03-29 | 青岛中科荣达新材料有限公司 | A kind of method that composite catalyst produces polyester modified dose of SIPE |
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| CN109503434A (en) * | 2018-11-16 | 2019-03-22 | 泰山医学院 | A kind of multicomponent process for catalytic synthesis of the modifying agent M-phthalic acid dipropylene glycol ester -5- sodium sulfonate of polyester PTT |
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| CN109535041A (en) * | 2018-11-22 | 2019-03-29 | 青岛中科荣达新材料有限公司 | A kind of method that composite catalyst produces polyester modified dose of SIPE |
| CN109535041B (en) * | 2018-11-22 | 2021-08-10 | 青岛中科荣达新材料有限公司 | Method for producing polyester modifier SIPE (styrene-isoprene-styrene) by using composite catalyst |
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| CN114085365B (en) * | 2021-10-25 | 2023-09-15 | 会通新材料(上海)有限公司 | Halogen-free flame-retardant thermoplastic polyester elastomer and preparation method thereof |
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